CN1016423B - The Catalysts and its preparation method that is used for synthetic Atactic Polypropelene - Google Patents

The Catalysts and its preparation method that is used for synthetic Atactic Polypropelene

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Publication number
CN1016423B
CN1016423B CN88103616.1A CN88103616A CN1016423B CN 1016423 B CN1016423 B CN 1016423B CN 88103616 A CN88103616 A CN 88103616A CN 1016423 B CN1016423 B CN 1016423B
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China
Prior art keywords
catalyzer
compound
ticl
atactic polypropelene
magnesium
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CN88103616.1A
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CN1030082A (en
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蒂莫·赖农伦
帕卡·索慕伦
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Neste Oyj
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Neste Oyj
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Publication of CN1030082A publication Critical patent/CN1030082A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene

Abstract

Employing is made the ziegler-natta catalyst system of carrier by the chlorating dialkyl magnesium compound, makes propylene carry out slurry polymerization and generates Atactic Polypropelene.During the preparation catalyst system, with the hot TiCl of above-mentioned solid composition 4Solution carries out reflow treatment, products therefrom is added in the reaction system under slurry polymerization conditions with trialkylaluminium again.To obtain unregulated polymer.

Description

The Catalysts and its preparation method that is used for synthetic Atactic Polypropelene
The invention relates to Ziegler-Natta catalyst of being mainly used in synthetic Atactic Polypropelene and preparation method thereof.Utilize this catalyzer can synthesize Atactic Polypropelene at an easy rate.
A large amount of examples in the patent documentation have all been introduced can be in order to MgCl 2Catalyzer synthesing isotactic polypropylene for carrier.Make the raw material of carrier and can directly use MgCl 2, perhaps adopt with chlorination reagent (as alkyl chloride, HCl, CCl 4Deng) reaction, general formula is MgClR or MgR 2Organo-magnesium compound.
Utilize mechanical means as grinding, or chemical process handle again with titanium compound as handling with alcohol earlier, can be with MgCl 2Activation forms the crystal with catalytic activity.Because the purpose product is an isotatic polypropylene, so in a certain step of preparation catalyzer, add a kind of stereoselective reagent (a kind of so-called in to body) that improves always, catalyzer is carried out obtaining having active Ziegler-Natta catalyst after the activation treatment with aluminum alkyls or alkyl aluminum chloride as ethyl benzoate (EtOBz), and in order to reach higher degree of isotacticity (＞96%), above-mentioned catalyzer need add another kind of electron donor(ED) (so-called external electronic donor) again in the aluminium treating processes.These make the Preparation of catalysts process complicated for body and activation step, and can not make a kind of catalyzer of main synthetic Atactic Polypropelene with this class catalyzer.Existing in the prior art with the MgCl that grinds 2* TiCl 4The technology of the synthetic Atactic Polypropelene of catalyzer, (Angew Makromol.Chem.120(1984) 73～90).But degree of isotacticity only has an appointment 20%.GB1335887(Montecatini Edison, 1970,10 29 applications) MgCl with polishing preparation is also disclosed 2* TiCl 4Catalyzer, its degree of isotacticity are 26.5%(heptane extraction process), catalyst activity is about 2kg polymkeric substance/g catalyzer.The method of the catalyzer of the synthetic Atactic Polypropelene of preparation also comprises MgCl in this article 2With 3TiCl 3* AlCl 3Grind together, but the catalyst activity of making like this is very low.Also to add additive (EtOBz, BuNH during grinding 2), increase and (reach 44%, but add behind the additive degree of isotacticity referring to JP59/43008A 2, TOyo Soda MfgCo).
Also useful Mg-alkylate is made the catalyzer of the synthetic Atactic Polypropelene of feedstock production.But can positive instance seldom, and wherein arbitrary activity of such catalysts all can not be compared with catalyst activity of the present invention.In the above-mentioned example, be to adopt alkyl magnesium or green reagent with TiCl 4Be reduced into TiCl 3Catalyzer for base.Work as TiCl 4During with dialkyl magnesium or the reaction of halogenated alkyl magnesium compound, obtain containing TiCl 3Catalyzer, its activity is lower than the activity of magnesium chloride supported catalyst.Do not see as yet and dialkyl magnesium is carried out chloridized make it become MgCl 2Example.
DE2751807(Veba-Chemie AG, 1979) method that prepare catalyzer in is quite complicated, and this method adopts magnesium sheet to make raw material, and its and monobromethane are reacted in ethereal solution, generation MgEtBr, and wherein EtMg uses TiCl again according to the formation of Schlenk balanced type 4Carrying out titanizing handles.With through catalyzer composition and DEAC(diethyl aluminum chloride) polypropylene (degree of isotacticity＜20%) amount of activatory catalyzer " random basically " that synthesize seldom, have only 0.5～1.5kg/g catalyzer.
BE883637-US4276191(Standard Oil Co.1980) with dibutylmagnesium/triethyl aluminum complex compound and titanium tetrachloride reaction, adding DEAC carries out polymerization and obtains the very high polymkeric substance of degree of randomness in, but activity has only 126g polypropylene/g catalyzer.
US3933934(Naphtachimie, 1976) in MAGNESIUM METAL, iodine and just-chlorobutane reduction TiCl 4, obtain MgCl 2And TiCl 3Mixture.Can synthesize the very high polypropylene of degree of randomness (dissolving in heptane part 96～99%) with this catalyzer, but activity is too low, less than 1kg polymkeric substance/g catalyzer.
Preparation is applicable to when synthesizing the amorphous polyolefin catalyst, available alcoholization magnesium or magnesium hydroxide and TiCl 4Reaction is referring to US3951935(Hoechst AG, 1976).Can adopt SiCl 4Make additive.Because alkoxide and TiCl 4Reaction generates the chlorinating alcohols titanium, makes catalyst activity very low, is about 400g polymkeric substance/mmol.
Polymerizing catalyst of the present invention is by through chloride but can not titaniferous compound chlorination and use TiCl 4The dialkyl magnesium compound of solution-treated is formed, and this component is configured for preparing the active catalyst system of Atactic Polypropelene with a kind of promotor.The first step of preparation polymerizing catalyst of the present invention is that chlorination is dissolved in the dialkyl magnesium compound in anhydrous solvent such as the hydrocarbon solvent.Be easy to this solution is carried out chloridized with suitable chlorizating agent, as make gas chlorination agent bubblings such as chlorine or hydrogenchloride by this solution.Also available liquid chlorizating agent such as tetracol phenixin, chloroform, methylene dichloride, alkyl chloride (as chlorobutane) etc. carry out chloridized to dialkyl magnesium compound.Be that anhydrous solvent washs chlorizate several times with exsiccant then, the same hydrocarbon solvent of the preferably above-mentioned dissolved magnesium compound of solvent of washing usefulness.This chlorating dialkyl magnesium compound is also referred to as carrier, again through TiCl 4Handle, even carrier compound and liquid TiCl 4Solution refluxed several hours under 80～100 ℃ intensification together, as 2～4 hours.General constituent content is (only having surveyed most important constituent content) Mg=15～21Wt% in the product after the processing, Ti=2～10Wt%, Cl=30～65Wt%.
The catalyzer that impels and keep polyreaction is made up of catalyst component and a kind of promotor that carrier and Ti compound are constituted, the most handy trialkylaluminium cocatalyst during synthetic Atactic Polypropelene.
Can under various polymerizing conditions, carry out polymerization with this catalyzer, but best with slurry polymerization process, being about to catalyzer and monomer and being added in the suitable liquor, polymkeric substance forms slurry because of being insoluble to this liquid.
The present invention and above-mentioned reference and all polypropylene catalyst patented technologies are compared, can obtain following result.(a) it is generally acknowledged that in patent documentation what need is isotatic polypropylene (wherein containing the polymkeric substance that dissolves in heptane less than 10～20%); (b) need not any electron donor(ED) in the catalyzer of the present invention; (c) though also use MgCl in the prior art 2And partly prepare Atactic Polypropelene with alkyl magnesium, but do not have one fen Patent publish when the support of the catalyst of the synthetic Atactic Polypropelene of preparation, clearly adopting aforesaid method, the alkyl magnesium chloride compound is made carrier, and then makes this carrier and titanium compound reaction.Be that chlorinated cpds is not as TiCl 4Titaniferous like this compound is because titanium-containing compound can generate TiCl 3, cause active the reduction.(d) do not need to resemble and use MgCl in the past 2Preparation during catalyzer be make catalyzer and grinding carrier, so preparation process is very simple, catalyzer can prepare in a reactor, whole process only needs two-step reaction (chlorination and titanizing).
Atactic Polypropelene is a kind of simple amorphous polyolefine.Because of its amorphous state has surfactant property, its purposes is exactly based on this characteristic.For example, it can be used to heat melten gel, lamination glue, filled cable really, as the bituminous additive or replace pitch fully as roof Material, glue card, pugging at anti-corrosion additive, wall-wall tapestry, reach in various crystal and the sealing combination, as the tackiness agent composition.Also can be used as matrix material, the damp proof material in building the road and the line material on the various traffic road surface.Also can be used as cheap filler and/or elastomeric properties-correcting agent.
Atactic Polypropelene also can be added in the molding plaster, makes its waterproof.Also can be added in the laminated product of food product pack,, and meet the relevant regulations of food product pack because of it is nontoxic.
Can be used as additive in the lubricating oil through maleic anhydride modified Atactic Polypropelene.By utilizing superoxide, after Atactic Polypropelene and the polyhutadiene grafting, be suitable for making film, tubing, part, laminate or fiber.
Atactic polyolefin also comprises Atactic Polypropelene certainly, can be used in the self-adhesive tape, in the moistureproof heat-resisting and electrically insulating material, in the ink, as oil absorber, and is used in the goods of colding pressing.
Can be by the described catalyzer that is prepared of following example.
Example 1,
With 100mlBOMAG(butyl octyl magnesium), 20% n-heptane solution, (Schering AG) is added in the 1 liter of glass reactor that disposes agitator, thermometer and reflux exchanger.All reinforced and treating processess are all carried out in purity nitrogen atmosphere (99.999%), adding is through the 100ml of molecular sieve drying heptane, make dry chlorine gas in 30 minutes, bubbling passes through mixed solution between 20～32 ℃, after the brown precipitate usefulness exsiccant heptane wash of separating out 4 times, leave standstill, heptane is siphon off.Again under 80～100 ℃, in 2 hours with 100ml heptane and 100ml TiCl 4Handle solid catalyst carrier.With warm heptane with the catalyst detergent that obtains 5 times after, staticly settle, extract heptane out with siphonage, dry under nitrogen gas stream again, contain in the solid catalyst: Mg 16.5Wt%, Ti 4.5Wt%, Cl 60.0Wt%.
Example 2
The dry heptane of 150ml BOMAG and 300ml is added in 1 liter of reactor,, reactor is put in ice/water-bath cool off, temperature is remained on 20～30 ℃, separate out light-yellow precipitate, led to nitrogen 30 minutes with dry HCl gas processing mixture 30 minutes.After adding the 300ml heptane, staticly settle, solution is siphon off.With catalyst detergent 4 times, in reactor, add 100mlTiCl as stated above 4With the 100ml heptane; Under 100 ℃, handled 2 hours with titanium.Add the 10ml heptane, staticly settle, solution is siphon off.With hot heptane wash catalyzer 5 times, at last that product is dry in vacuum and nitrogen gas stream.Contain Mg 10.2Wt% in the solid catalyst, Ti 2.3Wt%, Cl60.0Wt%.
Example 3
150mlBOMAG and the dried heptane of 300ml are added in 1 liter of reactor, slowly drip the 40mlCCl that is dissolved in the 40ml heptane from addition funnel 4Use the ice bath cooling reactor, temperature is remained on 10～35 ℃, 300ml heptane wash 4 times of the light brown of separating out precipitation.Under 100 ℃, use 100mlTiCl again 4Handled this support of the catalyst 2 hours with the 100ml heptane.It is dry in vacuum and nitrogen gas stream after the light red catalyzer that obtains is washed 4 times with hot heptane.Contain Mg21.0Wt% in the gained solid catalyst, Ti2.1Wt%, Cl62Wt%.
Example 4
In 1 liter of reactor, add 115mlDBM(14% dibutylmagnesium/Isopar E solution, Lithco Europe Ltd) and the 300ml heptane.Under 20～30 ℃, feed 20 minutes chlorine, the yellow mercury oxide of separating out carried out nitriding treatment 30 minutes, add the 600ml heptane, staticly settle to solution, behind the siphon off solution with 50mlTiCl 4Be added on the support of the catalyst with the 50ml heptane, temperature is raised to 92 ℃, and kept this temperature 2 hours,, dry under vacuum and in the nitrogen gas stream then with the hot heptane of 300ml with the catalyst detergent that obtains 4 times.Contain in the gained solid catalyst: Mg 17.1Wt%, Ti 5.5Wt%, Cl 59.8Wt%.
Polymerization
Under following slurry polymerization conditions, utilize the Mg/Ti composition in the example 1～5 to combine with triisobutyl aluminium, carry out propylene polymerization.Add the 630ml heptane to 2 liters of reactors, add the aluminum alkyls of 20ml, add catalyzer, with 50ml heptane flushing (cumulative volume 700ml) with a specific feed hopper with the heptane dilution with syringe.What aluminum alkyls adopted is triisobutyl aluminium, and Al/Ti is 100.Agitator is transferred to 500rpm feeds hydrogen, add the gaseous state monomer continuously and carry out polymerization.Polyreaction was carried out under 70 ℃ 3 hours.After polyreaction finishes, steam solvent in the product, put in the fume cupboard about 10 hours, adopt slowly heating modestly to proceed to evaporate (about 4 hours) till the whole fusions of polymkeric substance with 3 liters of decant glassworks.Stir carefully, product is poured in the aluminum die weighed.With the polymer fragment that is ground into diameter 3～5mm, in 6 hours, extract product (about 3g) when measuring the polymkeric substance degree of isotacticity with the ebullient heptane.
Table 1 example goes out the experimental result of polyreaction.
Table 1
Carry out polymerization experiment with catalyzer in the example
The propylene hydrogen activity
Example pressure, bar pressure, crust kg polypropylene/gram catalyzer degree of isotacticity %
1 8 3.6 7.8 22
2 8 3 5.2 28
3 8 3 5.7 37
4 8 3 4.0 25

Claims (13)

1, a kind of catalyzer that is used for synthetic Atactic Polypropelene is characterized in that being made up of the transition metal composition and the trialkylaluminium cocatalyst that are loaded on the following carrier, and this carrier is that a kind of elder generation carries out chlorination through chloride not titaniferous compound, again through TiCl 4The dialkyl magnesium compound of titanizing, no any electronic donor compound capable in the catalyzer.
2,, it is characterized in that said dialkyl magnesium compound is butyl octyl magnesium or dibutylmagnesium according to the catalyzer of claim 1.
3,, it is characterized in that chlorinated cpds is chlorine Cl according to the catalyzer of claim 1 2
4,, it is characterized in that chlorinated cpds is hydrogenchloride HCl according to the catalyzer of claim 1.
5,, it is characterized in that chlorinated cpds is tetracol phenixin CCl according to the catalyzer of claim 1 4
6, preparation is applicable to the method for the catalyzer of synthetic Atactic Polypropelene, it is characterized in that with chloride not titaniferous compound the dialkyl magnesium compound that dissolves in the anhydrous liquid hydrocarbon being carried out chloridized, the carrier compound that obtains thus liquid TiCl 4Carry out reflow treatment, the transition metal composition that obtains is mixed with trialkylaluminium, need not any electronic donor compound capable.
7,, it is characterized in that organo-magnesium compound is a dialkyl magnesium, preferably butyl octyl magnesium or dibutylmagnesium according to the method for claim 6.
8,, it is characterized in that chlorinated cpds is chlorine Cl according to the method for claim 6 2
9,, it is characterized in that chlorinated cpds is hydrogenchloride HCl according to the method for claim 6.
10,, it is characterized in that chlorinated cpds is tetracol phenixin CCl according to the method for claim 6 4
11, according to the method for arbitrary claim among the claim 6-10, it is characterized in that titanizing is handled carries out under about 8～100 ℃.
12,, it is characterized in that the titanizing treatment time is about 2～4 hours according to the method for arbitrary claim among the claim 6-10.
13,, it is characterized in that the titanizing treatment time is about 2～4 hours according to the method for claim 11.
CN88103616.1A 1987-05-25 1988-05-25 The Catalysts and its preparation method that is used for synthetic Atactic Polypropelene Expired CN1016423B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI872303A FI79123C (en) 1987-05-25 1987-05-25 CATALYS FOER FRAMSTAELLNING AV ATAKTISKT POLYPROPEN OCH FOERFARANDE FOER FRAMSTAELLNING AV EN DYLIK KATALYT.
FI872303 1987-05-25

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CN1030082A CN1030082A (en) 1989-01-04
CN1016423B true CN1016423B (en) 1992-04-29

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AT (1) ATE88192T1 (en)
DE (1) DE3880324D1 (en)
FI (1) FI79123C (en)
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JP4414506B2 (en) * 1998-05-22 2010-02-10 株式会社プライムポリマー Crystalline polypropylene and molded article and film thereof
US6639038B2 (en) 1998-05-22 2003-10-28 Idemitsu Petrochemical Co., Ltd. Crystalline polypropylene and its moldings and films
JP2002065541A (en) * 2000-08-24 2002-03-05 Nissen Chemitec Corp Oil absorbing mat, its manufacturing method, and rotating roller for manufacturing oil absorbing mat
CN1315885C (en) * 2005-04-26 2007-05-16 浙江大学 Catalast for polymerizing propylene with low carried titanium MgCl2/AlCl3 composite carrier and its preparation process
CA2557410C (en) * 2006-08-25 2014-01-28 Nova Chemicals Corporation Ziegler-natta catalyst for high temperature polymerization
BR112019006072B1 (en) * 2016-09-29 2023-02-14 Dow Global Technologies Llc METHOD OF POLYMERIZATION OF AN OLEFIN USING A ZIEGLER-NATTA CATALYST AND AN UNSUPPORTED MOLECULAR CATALYST IN THE SAME REACTOR AT THE SAME TIME AND POLYMERIZATION METHOD
FR3115790B1 (en) 2020-11-03 2023-07-07 Prochimir single layer monolithic breathable waterproof film

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FR2127368A5 (en) * 1971-03-05 1972-10-13 Naphtachimie Sa Atactic waxes - by copolymerising propylene and unsatd cpds in solvent with ziegler catalysts
BE794323A (en) * 1972-01-20 1973-07-19 Naphtachimie Sa PROCESS FOR THE MANUFACTURE OF ATACTIC POLYOLEFIN WAXES
DE2751807A1 (en) * 1977-11-19 1979-05-23 Veba Chemie Ag Ziegler-Natta catalyst for prodn. of atactic (co)polyolefin - produced from titanium tetra:chloride, organo-magnesium cpd. and organo-aluminium cpd.
US4276191A (en) * 1979-06-04 1981-06-30 Standard Oil Company (Indiana) Catalyst and process for polymerization of alpha-olefins
FR2567526B1 (en) * 1984-07-13 1987-02-06 Atochem PROCESS FOR THE PREPARATION OF A NEW TRANSITION METAL COMPONENT ON A POLYMERIC SUPPORT FOR A CATALYTIC POLYMERIZATION SYSTEM OF OLEFINS

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EP0394237B1 (en) 1993-04-14
NO890201D0 (en) 1989-01-17
FI79123C (en) 1989-11-10
CN1030082A (en) 1989-01-04
EP0394237A1 (en) 1990-10-31
NO890201L (en) 1989-01-17
FI872303A (en) 1988-11-26
FI872303A0 (en) 1987-05-25
FI79123B (en) 1989-07-31
JPH02502734A (en) 1990-08-30
ATE88192T1 (en) 1993-04-15
DE3880324D1 (en) 1993-05-19

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